US20040101761A1 - Solid electrolyte and battery employing the same - Google Patents

Solid electrolyte and battery employing the same Download PDF

Info

Publication number
US20040101761A1
US20040101761A1 US10/656,180 US65618003A US2004101761A1 US 20040101761 A1 US20040101761 A1 US 20040101761A1 US 65618003 A US65618003 A US 65618003A US 2004101761 A1 US2004101761 A1 US 2004101761A1
Authority
US
United States
Prior art keywords
solid electrolyte
thin
ionic conductivity
film
battery
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
US10/656,180
Other versions
US7220517B2 (en
Inventor
Young-sin Park
Seok-Soo Lee
Young-Gu Jin
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Samsung Electronics Co Ltd
Original Assignee
Samsung Electronics Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Samsung Electronics Co Ltd filed Critical Samsung Electronics Co Ltd
Assigned to SAMSUNG ELECTRONICS CO., LTD. reassignment SAMSUNG ELECTRONICS CO., LTD. ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: JIN, YOUNG-GU, LEE, SEOK-SOO, PARK, YOUNG-SIN
Publication of US20040101761A1 publication Critical patent/US20040101761A1/en
Application granted granted Critical
Publication of US7220517B2 publication Critical patent/US7220517B2/en
Active legal-status Critical Current
Adjusted expiration legal-status Critical

Links

Images

Classifications

    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0561—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of inorganic materials only
    • H01M10/0562—Solid materials
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
    • H01B1/06—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances
    • H01B1/12—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances organic substances
    • H01B1/122—Ionic conductors
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M6/00—Primary cells; Manufacture thereof
    • H01M6/14—Cells with non-aqueous electrolyte
    • H01M6/18—Cells with non-aqueous electrolyte with solid electrolyte
    • H01M6/185—Cells with non-aqueous electrolyte with solid electrolyte with oxides, hydroxides or oxysalts as solid electrolytes
    • H01M6/186—Only oxysalts-containing solid electrolytes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/04—Construction or manufacture in general
    • H01M10/0472—Vertically superposed cells with vertically disposed plates
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2300/00—Electrolytes
    • H01M2300/0017—Non-aqueous electrolytes
    • H01M2300/0065—Solid electrolytes
    • H01M2300/0068—Solid electrolytes inorganic
    • H01M2300/0071—Oxides
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M6/00—Primary cells; Manufacture thereof
    • H01M6/40—Printed batteries, e.g. thin film batteries
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

Definitions

  • the present invention relates to a solid electrolyte and a battery employing the solid electrolyte, and more particularly, to a solid electrolyte with improved ionic conductivity and electro-chemical stability and a lithium battery and a thin-film battery that employ the same.
  • Lithium batteries which are lightweight and have high energy density, are taking the initiative in the market as an energy source of typical portable information devices, such as notebook personal computers, personal digital assistants (PDAs), mobile phone terminals.
  • PDAs personal digital assistants
  • CMOS complementary metal oxide semiconductors
  • ICs smart integrated circuits
  • micro-sensors micro-robots
  • MEMS micro-electro mechanical systems
  • FIG. 1 shows the structure of a conventional thin-film battery.
  • a conventional thin-film battery basically includes a cathode 12 , an electrolyte 14 , and an anode 13 , which are sequentially deposited as films on a current collector 11 .
  • the conventional thin-film battery has a thickness of about 10 ⁇ m.
  • the conventional thin-film battery Since the anode 13 is arranged close to the cathode 12 , the conventional thin-film battery has advantages of higher current density, higher battery efficiency, and shorter migration distance of ions. Since ions can migrate across the battery more easily and rapidly, the amount of reactants can be cut down greatly. Another advantage of the conventional thin-film battery is that it is easier to vary the shape and size of batteries for particular purposes. Therefore, thin-film batteries are considered to be the most promising main power source for micro-electronic devices, MEMS devices, micro-sensors.
  • Thin-film batteries are manufactured by the same method as semiconductor manufacturing processes. Accordingly, a thin-film battery may be mounted as a back-up power source along with electronic circuits in a semiconductor chip such as a complementary metal oxide semiconductor memory chip. In other words, the dead space of electronic devices can be minimized with maximum space utilization efficiency when a thin-film battery is incorporated.
  • Various batteries with different voltage and capacitance can be implemented through proper designing and etching for serial and parallel connections, and thus they have wide applications.
  • Electrolyte materials such as LiSiCON, Li 4 SiO 4 —Li 3 PO 4 solid solution, Li 2 O—B 2 O 3 -SiO 2 , Lipon (lithium phosphorous oxynitride), etc. are considered to be suitable for thin-film batteries.
  • glass electrolytes with high isotropic conductivity in amorphous state are easier to process into thin film form compared to crystalline electrolytes.
  • the ionic conductivity of glass electrolytes varies depending on their composition, and the composition of thin film electrolytes can be easily adjusted during deposition.
  • the comparatively low ionic conductivity of glass solid electrolytes is not important in thin-film batteries.
  • the currently most attractive solid electrolyte for thin-film batteries is Lipon, which is disclosed by John B. Bates et al. in U.S. Pat. No. 5,338,625, entitled “Thin film Battery and Method for making the Same.”
  • the LiPON solid electrolyte which is manufactured with a Li 3 PO 4 target by radio frequency sputtering in a nitrogen atmosphere, has a high ionic conductivity of 2( ⁇ 1) ⁇ 10 ⁇ 6 S/cm.
  • the Lipon solid electrolyte forms a very stable interface with an anode or a cathode and allows the battery to less deteriorate during operation.
  • the Lipon solid electrolyte satisfies most requirements for use in thin-film batteries employing a solid electrolyte.
  • the present invention provides a solid electrolyte for high capacity thin-film lithium secondary batteries with higher charging/discharging rate and energy output and extended cycle life, the solid electrolyte having higher ionic conductivity than general oxide glass electrolytes.
  • the present invention also provides a method of manufacturing the solid electrolyte.
  • the present invention also provides a high capacity lithium battery and thin-film battery that employ the solid electrolyte and has higher charging/discharging rate and energy output and extended cycle life.
  • M is at least one selected from the group consisting of Nb, Ta, P, and W.
  • a reactant gas containing nitrogen may be used.
  • FIG. 1 shows the structure of a conventional thin-film battery
  • FIG. 2 is a graph of ionic conductivity versus nitrogen content for solid electrolytes containing Li 2 O, SiO 2 , and Nb 2 O 5 in a mole ratio of 70:35:5, which were manufactured in Example 2 according to the present invention.
  • FIG. 3 is a graph of current density versus potential difference illustrating a chemically stable potential range for batteries with solid electrolytes manufactured in Example 2 according to the present invention.
  • network formers can form glass alone and may be oxides of Si, P, B, Ge, As, and the like and calcogenides.
  • Glass consists of oxygen polyhedron chains with network former ions.
  • Li 2 O is added as a network modifier, two non-bridging oxygen atoms occur and two Li + ions approach the non-bridging oxygen atoms for electrical neutrality.
  • the continuous network structure of the SiO 4 polyhedrons is damaged to some extent and viscosity and glass transition temperature are reduced.
  • Ionic conductivity mainly originates from network modifier ions that have higher mobility than the covalently bonded network former ions. Considering the mobility of Li + ions and the local neutral condition near the non-bridging oxygen atoms, the migration of the Li + ions when an electric field is applied can be interpreted as being a result of the ions hopping between the non-bridging oxygen atoms. Therefore, in order to improve the ionic conductivity of glass solid electrolytes, higher charge carrier concentration and lower conduction activation energy are necessary.
  • Conduction activation energy includes a strain energy term, which is determined by the size of gap between the non-bridging oxygen atoms, and an electrostatic energy term, which arises from the attraction and repulsion generated when Li + ions pass through the glass network structure including both positive and negative ions.
  • oxides such as Nb 2 O 5 , Ta 2 O 5 , WO 3 , Li 3 PO 4 , and the like, are added into a Li 2 O—SiO 2 solid electrolyte, the glass has a more open structure, activation energy is reduced, and ionic conductivity is improved.
  • a third oxide is added into a Li 2 O—SiO 2 solid electrolyte to modify the glass structure of the electrolyte to induce effective ionic conduction.
  • a structural change of the glass electrolyte by the additive can be understood by modeling an ionic potential of the additive as Z/r, where Z denotes the atomic number of the ion and r denotes the ionic diameter.
  • the network structure of pure glass, without an additive, is a random but balanced array of covalently bonded polyhedrons.
  • a solid electrolyte according to the present invention is manufactured by adding at least one third additive selected from the group consisting of Nb 2 O 5 , Ta 2 O 5 , WO 3 , and Li 3 PO 4 , to a Li 2 O—SiO 2 solid electrolyte.
  • nitrogen gas is flowed into the solid electrolyte.
  • the solid electrolyte according to the present invention has formula (1) below:
  • M is at least one selected from the group consisting of Nb, Ta, P, and W.
  • the mole ratio of silicon (Si) to the other components, expressed by y, is less than 0.05, the amount of SiO 2 is too small to form a glass phase. If the mole ratio of silicon is greater than 0.15, the relative amount of Li 2 O, which contributes to ionic conduction, is reduced and ionic conductivity is lowered.
  • M in formula (1) above denotes a third additive compound selected from among Nb, Ta, P, and W.
  • the third additive compound is added in oxide form, i.e., Nb 2 O 5 , Ta 2 O 5 , WO 3 , or Li 3 PO 4 . If the mole ratio of M to the other components, expressed by z, is less than 0.016, the addition effect is trivial. If the mole ratio of M is greater than 0.05, phase separation occurs.
  • a preferred compound for M is Nb. Nb can effectively reduce the above-described strain energy term and the electrostatic energy term, which arises from the attraction and repulsion generated when conductive ions pass the glass network including both positive and negative ions.
  • a nitrogen atom may be added in the manufacture of the solid electrolyte according to the present invention to further enhance the ionic conductivity.
  • nitrogen has a smaller electronegativity than oxygen and forms a stronger covalent bond with silicon.
  • the electrostatic attraction of nitrogen to lithium ions is reduced and the ionic conductivity of the solid electrolyte is improved.
  • the present invention also provides a method of manufacturing the solid electrolyte. Any methods, such as simultaneous sputtering, electron beam deposition, ion beam deposition, chemical vapor deposition, and the like, can be applied to manufacture the solid electrolyte according to the present invention.
  • reactant gas may be partially or fully replaced with nitrogen gas to incorporate nitrogen into the solid electrolyte.
  • nitrogen gas for example, when simultaneous sputtering is applied to form the solid electrolyte, separate Li 2 O, SiO 2 , and Nb 2 O 5 ceramic targets are simultaneously sputtered with Ar and O 2 gases serving as reactants, to form the solid electrolyte as a thin film.
  • the reactant gases may be partially or fully replaced with N 2 gas to incorporate into nitrogen into the thin film.
  • the present invention also provides a lithium secondary battery and a thin-film battery that employ the solid electrolyte.
  • a cathodic collector is coated with an active material composition, V 2 O 5 , LiMn 2 O 4 , LiCoO 2 , LiNiO 2 , or MoO 3 , and dried to form a cathode with a cathode active material layer.
  • an anode active material such as lithium metal, a lithium alloy, or graphite, is applied to an anodic collector by roll pressing, to form an anode with an anode active material layer.
  • a plurality of stacks of the cathode, the solid electrolyte described above, the anode are stacked upon one another and sealed in a vacuum to provide a lithium secondary battery.
  • a cathode active material such as V 2 O 5 , LiMn 2 O 4 , LiCoO 2 , LiNiO 2 , or MoO 3
  • the solid electrolyte is deposited on the cathode active material layer in a vacuum.
  • An anode active material such as lithium metal, a lithium alloy, a silicon alloy, or a tin alloy, is deposited on the solid electrolyte by thermal deposition or spurring, to provide a thin-film battery.
  • a solid electrolyte thin film having a thickness of 4,000 ⁇ was manufactured on a silicon substrate using Li 2 O, SiO 2 , and Nb 2 O 5 targets, which were 2 inches in diameter.
  • argon gas was supplied at 10 mTorr and 20 sccm at a radio frequency (RF) power of 60W to deposit a platinum (Pt) thin film having a thickness of 1000 ⁇ on the silicon substrate.
  • RF radio frequency
  • the Li 2 O, SiO 2 , and Nb 2 O 5 targets were simultaneously sputtered in an argon-oxygen (16:4 in sccm) atmosphere at 5 mTorr, to form a 4000- ⁇ -thick thin film on the Pt thin film.
  • RF power applied to each of the Li 2 O, SiO 2 , and Nb 2 O 5 targets was adjusted within a range of 30-120W to manufacture thin films having different compositions.
  • a Pt thin film was deposited to a thickness of 1000 ⁇ by supplying argon gas at 10 mTorr and 20 sccm over a hard mask, which was placed on the solid electrolyte thin film, at an RF power of 60W.
  • the ionic conductivity is greater for electrolyte thin films containing more Li 2 O.
  • the ionic conductivity is smaller for the electrolyte thin film containing less Nb 2 O 5 .
  • the ionic conductivity is greatest for the electrolyte thin film containing Li 2 O, SiO 2 , and Nb 2 O 5 in a mole ratio of 70:20:10, at about 5 ⁇ 10 ⁇ 7 S/cm.
  • the reactant gases for simultaneous sputtering were replaced partially or fully with nitrogen under the same sputtering conditions as in Example 1.
  • the total flow rate of the reactant gases was 20 sccm, and the partial flow rate of nitrogen gas was varied in a range from 2 to 20 sccm.
  • the ionic conductivity is increased when a small amount of nitrogen is added.
  • the ionic conductivity is increased above eight times when only nitrogen gas is supplied.
  • oxide-based solid electrolyte thin films which had different compositions as in Example 1, were manufactured in the same manner as in Example 1, except that only nitrogen gas was supplied as a reactant gas during deposition to enhance ionic conductivity.
  • the results are shown in Table 3.
  • the solid electrolyte thin films which have the formula of Li x Si y Nb z O v N w where 0.3 ⁇ x ⁇ 0.46, 0.05 ⁇ y ⁇ 0.15, 0.016 ⁇ z ⁇ 0.05, 0.42 ⁇ v ⁇ 0.5, and 0 ⁇ w ⁇ 0.029, have an ionic conductivity greater than 1.0 ⁇ 10 ⁇ 6 S/cm.
  • the amounts of Li, Si, and Nb in the solid electrolyte thin films were measured using inductive coupled plasma-atomic emission spectroscopy (ICP), and the amounts of oxygen and nitrogen were measured using x-ray photoelectron spectroscopy (XPS).
  • ICP inductive coupled plasma-atomic emission spectroscopy
  • XPS x-ray photoelectron spectroscopy
  • Oxide-based solid electrolyte thin films containing nitrogen were manufactured in the same manner as in Example 2, except that Li 3 PO 4 instead of Nb 2 O 5 was used. Change in ionic conductivity with respect to composition of the solid electrolytes is shown in Table 4. TABLE 4 Composition (mol %) Ionic Conductivity Li 2 O SiO 2 Li 3 PO 4 (S/cm) 70 25 5 1.1 ⁇ 10 ⁇ 6 60 35 5 1.5 ⁇ 10 ⁇ 6 50 34 16 2.1 ⁇ 10 ⁇ 6
  • a solid electrolyte according to the present invention contains nitrogen and has improved lithium ion conductivity and electrochemical stability. With such a solid electrolyte according to the present invention, longer lifespan lithium secondary batteries or thin-film batteries with higher charging/discharging rate, improved charging/discharging cycle properties, and a more chemically stable interface between the electrolyte and their electrode can be manufactured.

Abstract

A solid electrolyte, a method of manufacturing the same, and a lithium battery and a thin-film battery that employ the solid electrolyte are provided. The solid electrolyte contains nitrogen to enhance the ionic conductivity and electrochemical stability of batteries.

Description

    BACKGROUND OF THE INVENTION
  • This application claims priority from Korean Patent Application No. 2002-74362, filed on Nov. 27, 2002, in the Korean Intellectual Property Office, the disclosure of which is incorporated herein in its entirety by reference. [0001]
  • 1. Field of the Invention [0002]
  • The present invention relates to a solid electrolyte and a battery employing the solid electrolyte, and more particularly, to a solid electrolyte with improved ionic conductivity and electro-chemical stability and a lithium battery and a thin-film battery that employ the same. [0003]
  • 2. Description of the Related Art [0004]
  • With rapid advance in computer technology and the mobile communications field, the development of digital, smaller, and multimedia information devices have been accelerated. Lithium batteries, which are lightweight and have high energy density, are taking the initiative in the market as an energy source of typical portable information devices, such as notebook personal computers, personal digital assistants (PDAs), mobile phone terminals. [0005]
  • The size of batteries can be a limiting factor to the minimization of such electronic information devices. For example, the size of complementary metal oxide semiconductors (CMOS), smart integrated circuits (ICs), micro-sensors, micro-robots are limited by the size of their battery. Based on the advances in semiconductor manufacturing processes and micro-electro mechanical systems (MEMS), the use of thin-film batteries as an energy source for next-generation micro-systems is expected to increase. [0006]
  • FIG. 1 shows the structure of a conventional thin-film battery. Referring to FIG. 1, a conventional thin-film battery basically includes a [0007] cathode 12, an electrolyte 14, and an anode 13, which are sequentially deposited as films on a current collector 11. The conventional thin-film battery has a thickness of about 10 μm.
  • Since the anode [0008] 13 is arranged close to the cathode 12, the conventional thin-film battery has advantages of higher current density, higher battery efficiency, and shorter migration distance of ions. Since ions can migrate across the battery more easily and rapidly, the amount of reactants can be cut down greatly. Another advantage of the conventional thin-film battery is that it is easier to vary the shape and size of batteries for particular purposes. Therefore, thin-film batteries are considered to be the most promising main power source for micro-electronic devices, MEMS devices, micro-sensors.
  • Thin-film batteries are manufactured by the same method as semiconductor manufacturing processes. Accordingly, a thin-film battery may be mounted as a back-up power source along with electronic circuits in a semiconductor chip such as a complementary metal oxide semiconductor memory chip. In other words, the dead space of electronic devices can be minimized with maximum space utilization efficiency when a thin-film battery is incorporated. Various batteries with different voltage and capacitance can be implemented through proper designing and etching for serial and parallel connections, and thus they have wide applications. [0009]
  • Unlike conventional lithium ion batteries, thin-film batteries require a perfect solid Li[0010] + conducting electrolyte. Electrolyte materials, such as LiSiCON, Li4SiO4—Li3PO4 solid solution, Li2O—B2O3-SiO2, Lipon (lithium phosphorous oxynitride), etc. are considered to be suitable for thin-film batteries.
  • Although the above-listed crystalline solid electrolytes are known as having effective Li[0011] + conductivity, inorganic compounds with complex crystalline structure are amorphous when deposited as a thin film and require high temperature thermal treatment for crystallization. Therefore, it is impractical to apply such inorganic compounds to manufacture thin-film batteries.
  • In contrast, glass electrolytes with high isotropic conductivity in amorphous state are easier to process into thin film form compared to crystalline electrolytes. The ionic conductivity of glass electrolytes varies depending on their composition, and the composition of thin film electrolytes can be easily adjusted during deposition. In addition, in thin-film batteries whose electrodes are spaced merely several micrometers apart, as low ionic conductivity as 10[0012] −7 S/cm is satisfactory for battery formation. Therefore, the comparatively low ionic conductivity of glass solid electrolytes is not important in thin-film batteries.
  • The currently most attractive solid electrolyte for thin-film batteries is Lipon, which is disclosed by John B. Bates et al. in U.S. Pat. No. 5,338,625, entitled “Thin film Battery and Method for making the Same.” The LiPON solid electrolyte, which is manufactured with a Li[0013] 3PO4 target by radio frequency sputtering in a nitrogen atmosphere, has a high ionic conductivity of 2(±1)×10−6 S/cm. In addition, the Lipon solid electrolyte forms a very stable interface with an anode or a cathode and allows the battery to less deteriorate during operation. The Lipon solid electrolyte satisfies most requirements for use in thin-film batteries employing a solid electrolyte.
  • However, the properties of the Lipon thin film are greatly dependent on processing parameters for thin film formation and the Lipon thin film lacks reproducibility (P. Birke et al., Materials for thin film batteries for application in silicon technology, Solid State Ionics 93 (1997), 1-15). For this reason, considerable time is required to solve such above-described problems before Lipon thin films can be mass produced. [0014]
  • Therefore, for the development of thin-film batteries as a powerful energy source of 21[0015] st century leading micro-systems, it is essential to develop glass solid electrolytes with improved ionic conductivity.
    • SUMMARY OF THE INVENTION
  • The present invention provides a solid electrolyte for high capacity thin-film lithium secondary batteries with higher charging/discharging rate and energy output and extended cycle life, the solid electrolyte having higher ionic conductivity than general oxide glass electrolytes. [0016]
  • The present invention also provides a method of manufacturing the solid electrolyte. [0017]
  • The present invention also provides a high capacity lithium battery and thin-film battery that employ the solid electrolyte and has higher charging/discharging rate and energy output and extended cycle life. [0018]
  • In accordance with an aspect of the present invention, there is provided a solid electrolyte of formula (1) below: [0019]
  • LixSiyMzOvNw  (1)
  • where 0.3≦x≦0.46, 0.05≦y≦0.15, 0.016≦z<0.05, 0.42≦v<0.5, 0≦w≦0.029, and M is at least one selected from the group consisting of Nb, Ta, P, and W. [0020]
  • In accordance with another aspect of the present invention, there is provided a method of manufacturing the above solid electrolyte using Li[0021] 2O, SiO2, and at least one selected from the group consisting of Nb2O5, Ta2O5, WO3, and Li3PO4 as source materials by one of simultaneous sputtering, electron beam deposition, ion beam deposition, and chemical vapor deposition. In the manufacture of the solid electrolyte, a reactant gas containing nitrogen may be used.
  • In accordance with another aspect of the present invention, there are provided a lithium battery and a thin-film battery that employ the above solid electrolyte.[0022]
    • BRIEF DESCRIPTION OF THE DRAWINGS
  • The above and other features and advantages of the present invention will become more apparent by describing in detail exemplary embodiments thereof with reference to the attached drawings in which: [0023]
  • FIG. 1 shows the structure of a conventional thin-film battery; [0024]
  • FIG. 2 is a graph of ionic conductivity versus nitrogen content for solid electrolytes containing Li[0025] 2O, SiO2, and Nb2O5 in a mole ratio of 70:35:5, which were manufactured in Example 2 according to the present invention; and
  • FIG. 3 is a graph of current density versus potential difference illustrating a chemically stable potential range for batteries with solid electrolytes manufactured in Example 2 according to the present invention.[0026]
    • DETAILED DESCRIPTION OF THE INVENTION
  • In general, network formers can form glass alone and may be oxides of Si, P, B, Ge, As, and the like and calcogenides. Glass consists of oxygen polyhedron chains with network former ions. When Li[0027] 2O is added as a network modifier, two non-bridging oxygen atoms occur and two Li+ ions approach the non-bridging oxygen atoms for electrical neutrality. As a result, the continuous network structure of the SiO4 polyhedrons is damaged to some extent and viscosity and glass transition temperature are reduced.
  • Such a structural change in glass by the addition of Li[0028] 2O is more significant in terms of ionic conductivity. Ionic conductivity mainly originates from network modifier ions that have higher mobility than the covalently bonded network former ions. Considering the mobility of Li+ ions and the local neutral condition near the non-bridging oxygen atoms, the migration of the Li+ ions when an electric field is applied can be interpreted as being a result of the ions hopping between the non-bridging oxygen atoms. Therefore, in order to improve the ionic conductivity of glass solid electrolytes, higher charge carrier concentration and lower conduction activation energy are necessary.
  • The ionic conductivity is greatly increased by adding a small amount of the network modifier Li[0029] 2O. The Li2O seems to increase the total concentration of conductive Li+ ions and to destroy the glass network structure strongly bonded by covalent bonds. Conduction activation energy includes a strain energy term, which is determined by the size of gap between the non-bridging oxygen atoms, and an electrostatic energy term, which arises from the attraction and repulsion generated when Li+ ions pass through the glass network structure including both positive and negative ions.
  • Therefore, in order to improve the conductivity of Li[0030] + ions, controlling the spatial and electrostatic structures of glass is most important. According to the present invention, it is attempted to improve the conductivity of Li+ ions by adding oxides, such as Nb2O5, Ta2O5, WO3, Li3PO4, and the like.
  • When oxides, such as Nb[0031] 2O5, Ta2O5, WO3, Li3PO4, and the like, are added into a Li2O—SiO2 solid electrolyte, the glass has a more open structure, activation energy is reduced, and ionic conductivity is improved.
  • In particular, according to the present invention, a third oxide is added into a Li[0032] 2O—SiO2 solid electrolyte to modify the glass structure of the electrolyte to induce effective ionic conduction. A structural change of the glass electrolyte by the additive can be understood by modeling an ionic potential of the additive as Z/r, where Z denotes the atomic number of the ion and r denotes the ionic diameter. The network structure of pure glass, without an additive, is a random but balanced array of covalently bonded polyhedrons. However, the greater the ionic potential of a material added to the glass is, the more neighboring ions, in the glass, within a predetermined distance are effected by an electrostatic force and the more unbalanced the network structure becomes. As a result, the glass structure is greatly modified.
  • A solid electrolyte according to the present invention is manufactured by adding at least one third additive selected from the group consisting of Nb[0033] 2O5, Ta2O5, WO3, and Li3PO4, to a Li2O—SiO2 solid electrolyte. Optionally, nitrogen gas is flowed into the solid electrolyte. The solid electrolyte according to the present invention has formula (1) below:
  • LixSiyMzOvNw  (1)
  • where 0.3≦x≦0.46, 0.05≦y≦0.15, 0.016≦z<0.05, 0.42≦v<0.5, 0≦w≦0.029, and M is at least one selected from the group consisting of Nb, Ta, P, and W. [0034]
  • In the solid electrolyte, if the mole ratio of lithium (Li) to the other components, expressed by x, is less than 0.3, the amount of mobile lithium ions is too low and the ionic conductivity is very small. If the mole ratio of lithium is greater than 0.46, the glass structure is excessively damaged and phase separation or partial or full crystallization occurs, so that a perfect glass phase cannot be formed. [0035]
  • If the mole ratio of silicon (Si) to the other components, expressed by y, is less than 0.05, the amount of SiO[0036] 2 is too small to form a glass phase. If the mole ratio of silicon is greater than 0.15, the relative amount of Li2O, which contributes to ionic conduction, is reduced and ionic conductivity is lowered.
  • M in formula (1) above denotes a third additive compound selected from among Nb, Ta, P, and W. The third additive compound is added in oxide form, i.e., Nb[0037] 2O5, Ta2O5, WO3, or Li3PO4. If the mole ratio of M to the other components, expressed by z, is less than 0.016, the addition effect is trivial. If the mole ratio of M is greater than 0.05, phase separation occurs. A preferred compound for M is Nb. Nb can effectively reduce the above-described strain energy term and the electrostatic energy term, which arises from the attraction and repulsion generated when conductive ions pass the glass network including both positive and negative ions.
  • Alternatively, a nitrogen atom may be added in the manufacture of the solid electrolyte according to the present invention to further enhance the ionic conductivity. This effect can be explained by reduction in ionic conduction activation energy due to a difference in electronegativity between nitrogen (=3.04) and oxygen (=3.44). In particular, nitrogen has a smaller electronegativity than oxygen and forms a stronger covalent bond with silicon. As a result, the electrostatic attraction of nitrogen to lithium ions is reduced and the ionic conductivity of the solid electrolyte is improved. [0038]
  • The present invention also provides a method of manufacturing the solid electrolyte. Any methods, such as simultaneous sputtering, electron beam deposition, ion beam deposition, chemical vapor deposition, and the like, can be applied to manufacture the solid electrolyte according to the present invention. [0039]
  • In the manufacture of the solid electrolyte, reactant gas may be partially or fully replaced with nitrogen gas to incorporate nitrogen into the solid electrolyte. For example, when simultaneous sputtering is applied to form the solid electrolyte, separate Li[0040] 2O, SiO2, and Nb2O5 ceramic targets are simultaneously sputtered with Ar and O2 gases serving as reactants, to form the solid electrolyte as a thin film. The reactant gases may be partially or fully replaced with N2 gas to incorporate into nitrogen into the thin film.
  • The present invention also provides a lithium secondary battery and a thin-film battery that employ the solid electrolyte. [0041]
  • As an example of manufacturing a lithium battery using the solid electrolyte according to the present invention, a cathodic collector is coated with an active material composition, V[0042] 2O5, LiMn2O4, LiCoO2, LiNiO2, or MoO3, and dried to form a cathode with a cathode active material layer. Separately, an anode active material, such as lithium metal, a lithium alloy, or graphite, is applied to an anodic collector by roll pressing, to form an anode with an anode active material layer. A plurality of stacks of the cathode, the solid electrolyte described above, the anode are stacked upon one another and sealed in a vacuum to provide a lithium secondary battery.
  • As an example of manufacturing a thin-film battery using the solid electrolyte according to the present invention, a cathode active material, such as V[0043] 2O5, LiMn2O4, LiCoO2, LiNiO2, or MoO3, is vacuum deposited on a current collector. Next, the solid electrolyte is deposited on the cathode active material layer in a vacuum. An anode active material, such as lithium metal, a lithium alloy, a silicon alloy, or a tin alloy, is deposited on the solid electrolyte by thermal deposition or spurring, to provide a thin-film battery.
  • The present invention will be described in greater detail with reference to the following examples. The following examples are for illustrative purposes and are not intended to limit the scope of the invention. [0044]
    • EXAMPLE 1
  • A solid electrolyte thin film having a thickness of 4,000 Å was manufactured on a silicon substrate using Li[0045] 2O, SiO2, and Nb2O5 targets, which were 2 inches in diameter.
  • After adjusting the initial vacuum level below 2×10[0046] −6 torr, argon gas was supplied at 10 mTorr and 20 sccm at a radio frequency (RF) power of 60W to deposit a platinum (Pt) thin film having a thickness of 1000 Å on the silicon substrate. Next, the Li2O, SiO2, and Nb2O5 targets were simultaneously sputtered in an argon-oxygen (16:4 in sccm) atmosphere at 5 mTorr, to form a 4000-Å-thick thin film on the Pt thin film.
  • RF power applied to each of the Li[0047] 2O, SiO2, and Nb2O5 targets was adjusted within a range of 30-120W to manufacture thin films having different compositions. To measure the ionic conductivity of the solid electrolyte thin films having different compositions, on each of the solid electrolyte thin films a Pt thin film was deposited to a thickness of 1000 Å by supplying argon gas at 10 mTorr and 20 sccm over a hard mask, which was placed on the solid electrolyte thin film, at an RF power of 60W.
  • Cells having a size of 5 mm×5 mm were manufactured with the solid electrolyte thin films, and ionic conductivity was measured by applying a current across two blocking electrodes using an impedance analyzer (IM6). The ionic conductivities of the solid electrolytes containing Li[0048] 2O, SiO2, and Nb2O5 in different mole ratios are shown in Table 1.
    TABLE 1
    Composition (mol %) Ionic Conductivity
    Li2O SiO2 Nb2O5 (S/cm)
    16 67 16 3.4 × 10−9
    58 13 29 5.7 × 10−8
    58 29 13 1.8 × 10−7
    67 16 16 2.2 × 10−7
    65 30 5 2.9 × 10−7
    70 20 10 5.0 × 10−7
    70 25 5 4.0 × 10−7
  • As is apparent from Table 1, the ionic conductivity is greater for electrolyte thin films containing more Li[0049] 2O. For electrolyte thin films containing the same amount of Li2O, the ionic conductivity is smaller for the electrolyte thin film containing less Nb2O5. The ionic conductivity is greatest for the electrolyte thin film containing Li2O, SiO2, and Nb2O5 in a mole ratio of 70:20:10, at about 5×10−7 S/cm.
    • EXAMPLE 2
  • In order to further enhance the ionic conductivity of the electrolyte thin film containing Li[0050] 2O, SiO2, and Nb2O5 in a mole ratio of 70:20:10, which was greatest at about 5×10−7 S/cm among the other electrolyte thin films of Example 1, the reactant gases for simultaneous sputtering were replaced partially or fully with nitrogen under the same sputtering conditions as in Example 1. The total flow rate of the reactant gases was 20 sccm, and the partial flow rate of nitrogen gas was varied in a range from 2 to 20 sccm.
  • Change in ionic conductivity with respect to flow rate of nitrogen gas for electrolyte thin films containing Li[0051] 2O, SiO2, and Nb2O5 in a mole ratio of 70:20:10 is shown in Table 2 and FIG. 2.
    TABLE 2
    Used Gas Ionic Conductivity
    Ar O2 N2 (S/cm)
    16 4 — 4.0 × 10−7
    16 2 2 5.0 × 10−7
    14 — 6 1.9 × 10−6
    10 — 10 2.1 × 10−6
    — — 20 3.0 × 10−6
  • As is apparent from Table 2, the ionic conductivity is increased when a small amount of nitrogen is added. The ionic conductivity is increased above eight times when only nitrogen gas is supplied. [0052]
  • In order to determine an electrochemically stable potential range of a lithium secondary battery employing the nitrogen-containing solid electrolyte of Example 2, lithium was deposited by thermal evaporation to form a counter electrode on the solid electrolyte thin film. A potential ranging from 0V to 6V was applied across the lithium electrode using a Potentiostat (EG & G 263A) to measure current density. The results are shown in FIG. 3. In FIG. 3, the current density does not exceed 5 μA/cm[0053] 2 at a potential level up to 5.5 V (vs Li/Li+). As a result, the electrochemically stable potential range is determined to be in a range of 0-5.5V (vs Li/Li+).
  • In addition, oxide-based solid electrolyte thin films, which had different compositions as in Example 1, were manufactured in the same manner as in Example 1, except that only nitrogen gas was supplied as a reactant gas during deposition to enhance ionic conductivity. The results are shown in Table 3. [0054]
    TABLE 3
    Composition (mol %) Ionic Conductivity
    Li2O SiO2 Nb2O5 (S/cm)
    70 25 5 3.0 × 10−6
    70 20 10 2.5 × 10−6
    67 16 16 2.0 × 10−6
    60 35 5 2.7 × 10−6
    60 30 10 2.8 × 10−6
    50 45 5 1.5 × 10−6
    50 40 10 2.2 × 10−6
    50 34 16 1.8 × 10−6
  • As is apparent from Table 3, the solid electrolyte thin films, which have the formula of Li[0055] xSiyNbzOvNw where 0.3≦x≦0.46, 0.05≦y≦0.15, 0.016≦z<0.05, 0.42≦v<0.5, and 0≦w≦0.029, have an ionic conductivity greater than 1.0×10−6 S/cm.
  • The amounts of Li, Si, and Nb in the solid electrolyte thin films were measured using inductive coupled plasma-atomic emission spectroscopy (ICP), and the amounts of oxygen and nitrogen were measured using x-ray photoelectron spectroscopy (XPS). [0056]
  • Evidently, in the oxide-based solid electrolytes with various compositions, their ionic conductivity can be improved greatly by adding a small amount of nitrogen. [0057]
    • EXAMPLE 3
  • Oxide-based solid electrolyte thin films containing nitrogen were manufactured in the same manner as in Example 2, except that Li[0058] 3PO4 instead of Nb2O5 was used. Change in ionic conductivity with respect to composition of the solid electrolytes is shown in Table 4.
    TABLE 4
    Composition (mol %) Ionic Conductivity
    Li2O SiO2 Li3PO4 (S/cm)
    70 25 5 1.1 × 10−6
    60 35 5 1.5 × 10−6
    50 34 16 2.1 × 10−6
  • As is apparent from Table 4, all of the electrolytes have an ionic conductivity greater than 1.0×10[0059] −6 S/cm.
  • As described above, a solid electrolyte according to the present invention contains nitrogen and has improved lithium ion conductivity and electrochemical stability. With such a solid electrolyte according to the present invention, longer lifespan lithium secondary batteries or thin-film batteries with higher charging/discharging rate, improved charging/discharging cycle properties, and a more chemically stable interface between the electrolyte and their electrode can be manufactured. [0060]
  • While the present invention has been particularly shown and described with reference to exemplary embodiments thereof, it will be understood by those of ordinary skill in the art that various changes in form and details may be made therein without departing from the spirit and scope of the present invention as defined by the following claims. [0061]

Claims (5)

What is claimed is:
1. A solid electrolyte having the formula of LixSiyMzOvNw where 0.3≦x≦0.46, 0.05≦y≦0.15, 0.016≦z<0.05, 0.42≦v<0.5, 0≦w≦0.029, and M is at least one selected from the group consisting of Nb, Ta, P, and W.
2. A method of manufacturing the solid electrolyte of claim 1 using Li2O, SiO2, and at least one selected from the group consisting of Nb2O5, Ta2O5, WO3, and Li3PO4 as source materials by one of simultaneous sputtering, electron beam deposition, ion beam deposition, and chemical vapor deposition.
3. The method of claim 2, wherein a reactant gas containing nitrogen is used.
4. A lithium battery employing the solid electrolyte of claim 1.
5. A thin-film battery employing the solid electrolyte of claim 1.
US10/656,180 2002-11-27 2003-09-08 Solid electrolyte and battery employing the same Active 2024-07-30 US7220517B2 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
KR1020020074362A KR100682883B1 (en) 2002-11-27 2002-11-27 Solid electrolyte and battery employing the same
KR2002-74362 2002-11-27

Publications (2)

Publication Number Publication Date
US20040101761A1 true US20040101761A1 (en) 2004-05-27
US7220517B2 US7220517B2 (en) 2007-05-22

Family

ID=32310867

Family Applications (1)

Application Number Title Priority Date Filing Date
US10/656,180 Active 2024-07-30 US7220517B2 (en) 2002-11-27 2003-09-08 Solid electrolyte and battery employing the same

Country Status (5)

Country Link
US (1) US7220517B2 (en)
EP (1) EP1427042B1 (en)
JP (1) JP3917126B2 (en)
KR (1) KR100682883B1 (en)
DE (1) DE60332084D1 (en)

Cited By (41)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2009094524A1 (en) * 2008-01-23 2009-07-30 Infinite Power Solutions, Inc. Thin film electrolyte for thin film batteries
US20100242265A1 (en) * 2007-08-13 2010-09-30 University Of Virginia Patent Foundation Thin film battery synthesis by directed vapor deposition
US7959769B2 (en) 2004-12-08 2011-06-14 Infinite Power Solutions, Inc. Deposition of LiCoO2
US7993773B2 (en) 2002-08-09 2011-08-09 Infinite Power Solutions, Inc. Electrochemical apparatus with barrier layer protected substrate
US8021778B2 (en) 2002-08-09 2011-09-20 Infinite Power Solutions, Inc. Electrochemical apparatus with barrier layer protected substrate
US8062708B2 (en) 2006-09-29 2011-11-22 Infinite Power Solutions, Inc. Masking of and material constraint for depositing battery layers on flexible substrates
US20120141866A1 (en) * 2010-12-07 2012-06-07 Semiconductor Energy Laboratory Co., Ltd. Power storage device
US8197781B2 (en) 2006-11-07 2012-06-12 Infinite Power Solutions, Inc. Sputtering target of Li3PO4 and method for producing same
US8236443B2 (en) 2002-08-09 2012-08-07 Infinite Power Solutions, Inc. Metal film encapsulation
US20120219842A1 (en) * 2003-10-14 2012-08-30 Polyplus Battery Company Protected lithium electrodes having tape cast ceramic and glass-ceramic membranes
US8260203B2 (en) 2008-09-12 2012-09-04 Infinite Power Solutions, Inc. Energy device with integral conductive surface for data communication via electromagnetic energy and method thereof
US8268488B2 (en) 2007-12-21 2012-09-18 Infinite Power Solutions, Inc. Thin film electrolyte for thin film batteries
US8350519B2 (en) 2008-04-02 2013-01-08 Infinite Power Solutions, Inc Passive over/under voltage control and protection for energy storage devices associated with energy harvesting
US8394522B2 (en) 2002-08-09 2013-03-12 Infinite Power Solutions, Inc. Robust metal film encapsulation
US8404376B2 (en) 2002-08-09 2013-03-26 Infinite Power Solutions, Inc. Metal film encapsulation
US8431264B2 (en) 2002-08-09 2013-04-30 Infinite Power Solutions, Inc. Hybrid thin-film battery
US8445130B2 (en) 2002-08-09 2013-05-21 Infinite Power Solutions, Inc. Hybrid thin-film battery
US8508193B2 (en) 2008-10-08 2013-08-13 Infinite Power Solutions, Inc. Environmentally-powered wireless sensor module
US8518581B2 (en) 2008-01-11 2013-08-27 Inifinite Power Solutions, Inc. Thin film encapsulation for thin film batteries and other devices
US8599572B2 (en) 2009-09-01 2013-12-03 Infinite Power Solutions, Inc. Printed circuit board with integrated thin film battery
US8636876B2 (en) 2004-12-08 2014-01-28 R. Ernest Demaray Deposition of LiCoO2
US8728285B2 (en) 2003-05-23 2014-05-20 Demaray, Llc Transparent conductive oxides
US8906523B2 (en) 2008-08-11 2014-12-09 Infinite Power Solutions, Inc. Energy device with integral collector surface for electromagnetic energy harvesting and method thereof
US9123941B2 (en) 2004-02-06 2015-09-01 Polyplus Battery Company Protected active metal electrode and battery cell structures with non-aqueous interlayer architecture
US9183995B2 (en) 2012-06-01 2015-11-10 Semiconductor Energy Laboratory Co., Ltd. Negative electrode for power storage device and power storage device
US9334557B2 (en) 2007-12-21 2016-05-10 Sapurast Research Llc Method for sputter targets for electrolyte films
US9362538B2 (en) 2002-10-15 2016-06-07 Polyplus Battery Company Advanced lithium ion batteries based on solid state protected lithium electrodes
US9368775B2 (en) 2004-02-06 2016-06-14 Polyplus Battery Company Protected lithium electrodes having porous ceramic separators, including an integrated structure of porous and dense Li ion conducting garnet solid electrolyte layers
US9384904B2 (en) 2012-04-06 2016-07-05 Semiconductor Energy Laboratory Co., Ltd. Negative electrode for power storage device, method for forming the same, and power storage device
US9634296B2 (en) 2002-08-09 2017-04-25 Sapurast Research Llc Thin film battery on an integrated circuit or circuit board and method thereof
US9660265B2 (en) 2011-11-15 2017-05-23 Polyplus Battery Company Lithium sulfur batteries and electrolytes and sulfur cathodes thereof
US9799461B2 (en) 2011-09-02 2017-10-24 Semiconductor Energy Laboratory Co., Ltd. Power storage device and method for manufacturing electrode
US9905860B2 (en) 2013-06-28 2018-02-27 Polyplus Battery Company Water activated battery system having enhanced start-up behavior
US10084168B2 (en) * 2012-10-09 2018-09-25 Johnson Battery Technologies, Inc. Solid-state battery separators and methods of fabrication
US10333123B2 (en) 2012-03-01 2019-06-25 Johnson Ip Holding, Llc High capacity solid state composite cathode, solid state composite separator, solid-state rechargeable lithium battery and methods of making same
US10388467B2 (en) 2012-11-07 2019-08-20 Semiconductor Energy Laboratory Co., Ltd. Electrode for power storage device, power storage device, and manufacturing method of electrode for power storage device
US10566611B2 (en) 2015-12-21 2020-02-18 Johnson Ip Holding, Llc Solid-state batteries, separators, electrodes, and methods of fabrication
US10658661B2 (en) 2011-08-30 2020-05-19 Semiconductor Energy Laboratory Co., Ltd. Power storage device and method for manufacturing electrode
US10680277B2 (en) 2010-06-07 2020-06-09 Sapurast Research Llc Rechargeable, high-density electrochemical device
CN113308677A (en) * 2021-05-26 2021-08-27 南京理工大学北方研究院 Preparation method of nitrogen-doped amorphous niobium pentoxide film, lithium ion battery anode of all-solid-state film and lithium ion battery
USRE49205E1 (en) 2016-01-22 2022-09-06 Johnson Ip Holding, Llc Johnson lithium oxygen electrochemical engine

Families Citing this family (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20070012244A1 (en) * 2005-07-15 2007-01-18 Cymbet Corporation Apparatus and method for making thin-film batteries with soft and hard electrolyte layers
CA2615479A1 (en) * 2005-07-15 2007-01-25 Cymbet Corporation Thin-film batteries with polymer and lipon electrolyte layers and methods
US7776478B2 (en) * 2005-07-15 2010-08-17 Cymbet Corporation Thin-film batteries with polymer and LiPON electrolyte layers and method
JP5487577B2 (en) * 2008-08-26 2014-05-07 セイコーエプソン株式会社 Battery and battery manufacturing method
CN102414874A (en) * 2009-04-13 2012-04-11 应用材料公司 Composite materials containing metallized carbon nanotubes and nanofibers
US10658705B2 (en) 2018-03-07 2020-05-19 Space Charge, LLC Thin-film solid-state energy storage devices
US9853325B2 (en) 2011-06-29 2017-12-26 Space Charge, LLC Rugged, gel-free, lithium-free, high energy density solid-state electrochemical energy storage devices
US11527774B2 (en) 2011-06-29 2022-12-13 Space Charge, LLC Electrochemical energy storage devices
US10601074B2 (en) 2011-06-29 2020-03-24 Space Charge, LLC Rugged, gel-free, lithium-free, high energy density solid-state electrochemical energy storage devices
EP2744478A4 (en) 2011-08-17 2015-07-29 Basf Corp Marine based cosmetic active ingredients and use thereof
CN104272519B (en) * 2012-04-18 2017-06-30 应用材料公司 Pinhole-free solid electrolyte with high ion conductivity
US9603790B2 (en) 2012-11-15 2017-03-28 Basf Corporation Cosmetic compositions comprising marine plants
JP6165546B2 (en) * 2013-08-09 2017-07-19 株式会社日立製作所 Solid electrolyte and all-solid lithium ion secondary battery

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4555456A (en) * 1983-05-26 1985-11-26 Hitachi, Ltd. Cathode structure for thin film battery
US4572873A (en) * 1982-09-13 1986-02-25 Hitachi, Ltd. Titanium disulfide thin film and process for fabricating the same
US4645726A (en) * 1984-11-26 1987-02-24 Hitachi, Ltd. Solid state lithium battery
US4906537A (en) * 1987-10-22 1990-03-06 Minolta Camera Kabushiki Kaisha Secondary cell
USRE34469E (en) * 1987-06-18 1993-12-07 Eic Laboratories, Inc. Solid state electrochromic light modulator
US5755940A (en) * 1994-06-13 1998-05-26 Mitsui Petrochemical Industries, Ltd. Lithium ionic conducting glass thin film and carbon dioxide sensor comprising the glass thin film
US6770176B2 (en) * 2002-08-02 2004-08-03 Itn Energy Systems. Inc. Apparatus and method for fracture absorption layer

Family Cites Families (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS57172661A (en) * 1981-04-17 1982-10-23 Toshiba Corp Solid lithium battery
US5085953A (en) * 1990-09-18 1992-02-04 Eveready Battery Company, Inc. Vitreous compositions based on Li3 PO4 and LiPO3 as network formers and network modifiers
US5338625A (en) * 1992-07-29 1994-08-16 Martin Marietta Energy Systems, Inc. Thin film battery and method for making same
JPH08239218A (en) * 1995-03-01 1996-09-17 Mitsui Petrochem Ind Ltd Oxide composition and solid electrolyte
KR100385485B1 (en) * 2001-01-30 2003-05-27 백홍구 Thin film electrolyte and a method for preparing the same
KR100533933B1 (en) * 2002-06-07 2005-12-06 강원대학교산학협력단 Solid electrolyte and a method for preparing the same

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4572873A (en) * 1982-09-13 1986-02-25 Hitachi, Ltd. Titanium disulfide thin film and process for fabricating the same
US4555456A (en) * 1983-05-26 1985-11-26 Hitachi, Ltd. Cathode structure for thin film battery
US4645726A (en) * 1984-11-26 1987-02-24 Hitachi, Ltd. Solid state lithium battery
USRE34469E (en) * 1987-06-18 1993-12-07 Eic Laboratories, Inc. Solid state electrochromic light modulator
US4906537A (en) * 1987-10-22 1990-03-06 Minolta Camera Kabushiki Kaisha Secondary cell
US5755940A (en) * 1994-06-13 1998-05-26 Mitsui Petrochemical Industries, Ltd. Lithium ionic conducting glass thin film and carbon dioxide sensor comprising the glass thin film
US6770176B2 (en) * 2002-08-02 2004-08-03 Itn Energy Systems. Inc. Apparatus and method for fracture absorption layer

Cited By (66)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8236443B2 (en) 2002-08-09 2012-08-07 Infinite Power Solutions, Inc. Metal film encapsulation
US8535396B2 (en) 2002-08-09 2013-09-17 Infinite Power Solutions, Inc. Electrochemical apparatus with barrier layer protected substrate
US9634296B2 (en) 2002-08-09 2017-04-25 Sapurast Research Llc Thin film battery on an integrated circuit or circuit board and method thereof
US7993773B2 (en) 2002-08-09 2011-08-09 Infinite Power Solutions, Inc. Electrochemical apparatus with barrier layer protected substrate
US8445130B2 (en) 2002-08-09 2013-05-21 Infinite Power Solutions, Inc. Hybrid thin-film battery
US8431264B2 (en) 2002-08-09 2013-04-30 Infinite Power Solutions, Inc. Hybrid thin-film battery
US9793523B2 (en) 2002-08-09 2017-10-17 Sapurast Research Llc Electrochemical apparatus with barrier layer protected substrate
US8021778B2 (en) 2002-08-09 2011-09-20 Infinite Power Solutions, Inc. Electrochemical apparatus with barrier layer protected substrate
US8404376B2 (en) 2002-08-09 2013-03-26 Infinite Power Solutions, Inc. Metal film encapsulation
US8394522B2 (en) 2002-08-09 2013-03-12 Infinite Power Solutions, Inc. Robust metal film encapsulation
US9362538B2 (en) 2002-10-15 2016-06-07 Polyplus Battery Company Advanced lithium ion batteries based on solid state protected lithium electrodes
US8728285B2 (en) 2003-05-23 2014-05-20 Demaray, Llc Transparent conductive oxides
US9419299B2 (en) * 2003-10-14 2016-08-16 Polyplus Battery Company Battery cells with lithium ion conducting tape-cast ceramic, glass and glass-ceramic membranes
US9136568B2 (en) * 2003-10-14 2015-09-15 Polyplus Battery Company Protected lithium electrodes having tape cast ceramic and glass-ceramic membranes
US20120219842A1 (en) * 2003-10-14 2012-08-30 Polyplus Battery Company Protected lithium electrodes having tape cast ceramic and glass-ceramic membranes
US9601779B2 (en) 2003-10-14 2017-03-21 Polyplus Battery Company Battery cells with lithium ion conducting tape-cast ceramic, glass and glass-ceramic membranes
US9368775B2 (en) 2004-02-06 2016-06-14 Polyplus Battery Company Protected lithium electrodes having porous ceramic separators, including an integrated structure of porous and dense Li ion conducting garnet solid electrolyte layers
US9123941B2 (en) 2004-02-06 2015-09-01 Polyplus Battery Company Protected active metal electrode and battery cell structures with non-aqueous interlayer architecture
US10529971B2 (en) 2004-02-06 2020-01-07 Polyplus Battery Company Safety enhanced li-ion and lithium metal battery cells having protected lithium electrodes with enhanced separator safety against dendrite shorting
US9666850B2 (en) 2004-02-06 2017-05-30 Polyplus Battery Company Safety enhanced Li-ion and lithium metal battery cells having protected lithium electrodes with enhanced separator safety against dendrite shorting
US10916753B2 (en) 2004-02-06 2021-02-09 Polyplus Battery Company Lithium metal—seawater battery cells having protected lithium electrodes
US11646472B2 (en) 2004-02-06 2023-05-09 Polyplus Battery Company Making lithium metal—seawater battery cells having protected lithium electrodes
US7959769B2 (en) 2004-12-08 2011-06-14 Infinite Power Solutions, Inc. Deposition of LiCoO2
US8636876B2 (en) 2004-12-08 2014-01-28 R. Ernest Demaray Deposition of LiCoO2
US8062708B2 (en) 2006-09-29 2011-11-22 Infinite Power Solutions, Inc. Masking of and material constraint for depositing battery layers on flexible substrates
US8197781B2 (en) 2006-11-07 2012-06-12 Infinite Power Solutions, Inc. Sputtering target of Li3PO4 and method for producing same
US8784512B2 (en) * 2007-08-13 2014-07-22 University Of Virginia Patent Foundation Thin film battery synthesis by directed vapor deposition
US20100242265A1 (en) * 2007-08-13 2010-09-30 University Of Virginia Patent Foundation Thin film battery synthesis by directed vapor deposition
US9334557B2 (en) 2007-12-21 2016-05-10 Sapurast Research Llc Method for sputter targets for electrolyte films
US8268488B2 (en) 2007-12-21 2012-09-18 Infinite Power Solutions, Inc. Thin film electrolyte for thin film batteries
US8518581B2 (en) 2008-01-11 2013-08-27 Inifinite Power Solutions, Inc. Thin film encapsulation for thin film batteries and other devices
US9786873B2 (en) 2008-01-11 2017-10-10 Sapurast Research Llc Thin film encapsulation for thin film batteries and other devices
WO2009094524A1 (en) * 2008-01-23 2009-07-30 Infinite Power Solutions, Inc. Thin film electrolyte for thin film batteries
US8350519B2 (en) 2008-04-02 2013-01-08 Infinite Power Solutions, Inc Passive over/under voltage control and protection for energy storage devices associated with energy harvesting
US8906523B2 (en) 2008-08-11 2014-12-09 Infinite Power Solutions, Inc. Energy device with integral collector surface for electromagnetic energy harvesting and method thereof
US8260203B2 (en) 2008-09-12 2012-09-04 Infinite Power Solutions, Inc. Energy device with integral conductive surface for data communication via electromagnetic energy and method thereof
US8508193B2 (en) 2008-10-08 2013-08-13 Infinite Power Solutions, Inc. Environmentally-powered wireless sensor module
US9532453B2 (en) 2009-09-01 2016-12-27 Sapurast Research Llc Printed circuit board with integrated thin film battery
US8599572B2 (en) 2009-09-01 2013-12-03 Infinite Power Solutions, Inc. Printed circuit board with integrated thin film battery
US10680277B2 (en) 2010-06-07 2020-06-09 Sapurast Research Llc Rechargeable, high-density electrochemical device
US10128498B2 (en) 2010-12-07 2018-11-13 Semiconductor Energy Laboratory Co., Ltd. Power storage device
CN103238240A (en) * 2010-12-07 2013-08-07 株式会社半导体能源研究所 Power storage device
US20120141866A1 (en) * 2010-12-07 2012-06-07 Semiconductor Energy Laboratory Co., Ltd. Power storage device
US9362556B2 (en) * 2010-12-07 2016-06-07 Semiconductor Energy Laboratory Co., Ltd. Power storage device
US10658661B2 (en) 2011-08-30 2020-05-19 Semiconductor Energy Laboratory Co., Ltd. Power storage device and method for manufacturing electrode
US9799461B2 (en) 2011-09-02 2017-10-24 Semiconductor Energy Laboratory Co., Ltd. Power storage device and method for manufacturing electrode
US9660265B2 (en) 2011-11-15 2017-05-23 Polyplus Battery Company Lithium sulfur batteries and electrolytes and sulfur cathodes thereof
US10333123B2 (en) 2012-03-01 2019-06-25 Johnson Ip Holding, Llc High capacity solid state composite cathode, solid state composite separator, solid-state rechargeable lithium battery and methods of making same
US9685653B2 (en) 2012-04-06 2017-06-20 Semiconductor Energy Laboratory Co., Ltd. Negative electrode for power storage device, method for forming the same, and power storage device
US11056678B2 (en) 2012-04-06 2021-07-06 Semiconductor Energy Laboratory Co., Ltd. Negative electrode for power storage device, method for forming the same, and power storage device
US10263243B2 (en) 2012-04-06 2019-04-16 Semiconductor Energy Laboratory Co., Ltd. Negative electrode for power storage device, method for forming the same, and power storage device
US9899660B2 (en) 2012-04-06 2018-02-20 Semiconductor Energy Laboratory Co., Ltd. Negative electrode for power storage device, method for forming the same, and power storage device
US11605804B2 (en) 2012-04-06 2023-03-14 Semiconductor Energy Laboratory Co., Ltd. Negative electrode for power storage device, method for forming the same, and power storage device
US9384904B2 (en) 2012-04-06 2016-07-05 Semiconductor Energy Laboratory Co., Ltd. Negative electrode for power storage device, method for forming the same, and power storage device
US9911971B2 (en) 2012-06-01 2018-03-06 Semiconductor Energy Laboratory Co., Ltd. Negative electrode for power storage device and power storage device
US9183995B2 (en) 2012-06-01 2015-11-10 Semiconductor Energy Laboratory Co., Ltd. Negative electrode for power storage device and power storage device
US10541409B2 (en) 2012-06-01 2020-01-21 Semiconductor Energy Laboratory Co., Ltd. Negative electrode for power storage device and power storage device
US9698412B2 (en) 2012-06-01 2017-07-04 Semiconductor Energy Laboratory Co., Ltd. Negative electrode for power storage device and power storage device
US9490080B2 (en) 2012-06-01 2016-11-08 Semiconductor Energy Laboratory Co., Ltd. Negative electrode for power storage device and power storage device
US10084168B2 (en) * 2012-10-09 2018-09-25 Johnson Battery Technologies, Inc. Solid-state battery separators and methods of fabrication
US10388467B2 (en) 2012-11-07 2019-08-20 Semiconductor Energy Laboratory Co., Ltd. Electrode for power storage device, power storage device, and manufacturing method of electrode for power storage device
US9905860B2 (en) 2013-06-28 2018-02-27 Polyplus Battery Company Water activated battery system having enhanced start-up behavior
US11417873B2 (en) 2015-12-21 2022-08-16 Johnson Ip Holding, Llc Solid-state batteries, separators, electrodes, and methods of fabrication
US10566611B2 (en) 2015-12-21 2020-02-18 Johnson Ip Holding, Llc Solid-state batteries, separators, electrodes, and methods of fabrication
USRE49205E1 (en) 2016-01-22 2022-09-06 Johnson Ip Holding, Llc Johnson lithium oxygen electrochemical engine
CN113308677A (en) * 2021-05-26 2021-08-27 南京理工大学北方研究院 Preparation method of nitrogen-doped amorphous niobium pentoxide film, lithium ion battery anode of all-solid-state film and lithium ion battery

Also Published As

Publication number Publication date
JP3917126B2 (en) 2007-05-23
KR20040046433A (en) 2004-06-05
KR100682883B1 (en) 2007-02-15
US7220517B2 (en) 2007-05-22
EP1427042A1 (en) 2004-06-09
JP2004179161A (en) 2004-06-24
EP1427042B1 (en) 2010-04-14
DE60332084D1 (en) 2010-05-27

Similar Documents

Publication Publication Date Title
US7220517B2 (en) Solid electrolyte and battery employing the same
US7094500B2 (en) Secondary battery
KR100382767B1 (en) Anode thin film for Lithium secondary battery and manufacturing method thereof
US6828063B2 (en) Anode thin film for lithium secondary battery
US5567210A (en) Method for making an electrochemical cell
US20170279155A1 (en) Electrochemical device stacks including interlayers for reducing interfacial resistance and over-potential
KR100389908B1 (en) Anode thin film for Lithium secondary battery
JP2005519425A (en) Secondary battery with permeable anode current collector
CN105900212A (en) Deposition of solid state electrolyte on electrode layers in electrochemical devices
JP2004127743A (en) Thin film battery
US20070042272A1 (en) Solid electrolyte and all solid state battery using the same
KR20040095848A (en) Thin negative electrode for lithium secondary battery and manufacturing method thereof
KR100495674B1 (en) A cathode thin film for all solid state battery, preparation method thereof, and lithium thin film battery using the same
EP3598562A1 (en) Secondary battery
KR20020085942A (en) Multi-layered Solid Electrolyte for High Charge/Discharge Rate, Thin Film Battery Using the Same and Fabrication Method thereof
KR100533933B1 (en) Solid electrolyte and a method for preparing the same
US10833326B2 (en) Low-voltage microbattery with vanadium-based cathode
KR20180023380A (en) Lithium ion battery and method of preparing the same
KR20020063681A (en) Thin film electrolyte and a method for preparing the same
KR100550208B1 (en) Fabrication Method of Nano Complex Electrode Comprising Electrode Material Joined with Solid Electrolyte for Thin Film Battery
KR20220150539A (en) Anode-free all solid state battery comprising solid electrolyte having high ion conductivity and surface-roughened anode current collector
WO2022122309A1 (en) ELECTROLYTE MATERIAL WITH LiPON-COATED PARTICLES, BATTERY CELL, AND METHOD FOR MANUFACTURING THE ELECTROLYTE MATERIAL

Legal Events

Date Code Title Description
AS Assignment

Owner name: SAMSUNG ELECTRONICS CO., LTD., KOREA, REPUBLIC OF

Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNORS:PARK, YOUNG-SIN;LEE, SEOK-SOO;JIN, YOUNG-GU;REEL/FRAME:014487/0035

Effective date: 20030908

STCF Information on status: patent grant

Free format text: PATENTED CASE

FPAY Fee payment

Year of fee payment: 4

FEPP Fee payment procedure

Free format text: PAYOR NUMBER ASSIGNED (ORIGINAL EVENT CODE: ASPN); ENTITY STATUS OF PATENT OWNER: LARGE ENTITY

FPAY Fee payment

Year of fee payment: 8

MAFP Maintenance fee payment

Free format text: PAYMENT OF MAINTENANCE FEE, 12TH YEAR, LARGE ENTITY (ORIGINAL EVENT CODE: M1553); ENTITY STATUS OF PATENT OWNER: LARGE ENTITY

Year of fee payment: 12